CN85100048B - Synthesis of poly-phenylenetherephthalamide having high molecular weight - Google Patents
Synthesis of poly-phenylenetherephthalamide having high molecular weight Download PDFInfo
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- CN85100048B CN85100048B CN85100048A CN85100048A CN85100048B CN 85100048 B CN85100048 B CN 85100048B CN 85100048 A CN85100048 A CN 85100048A CN 85100048 A CN85100048 A CN 85100048A CN 85100048 B CN85100048 B CN 85100048B
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Abstract
The present invention relates to the synthesis of poly(p-phenylene terephthalamide) with a high molecular weight, which belongs to the synthesis of macromolecular compounds. The polycondensation of p-phenylene diamine and terephthaloyl chloride is carried out in amide which is a double salt solution formed by an alkali metal and an alkaline earth metal halide to generate poly(p-phenylene terephthalamide) with a high molecular weight. For example, a logarithmic viscosity number of poly(p-phenylene terephthalamide) which is synthesized in N-methyl pyrrolidone-lithium chloride (LiCl)-calcium chloride (CaCl2) double salt solution can be stably enhanced above 7, and can be enhanced to 9 to 10 maximally. The method has the advantages of good solubility, few impurities, simple post-treatment and proper operation range.
Description
The technical field of the invention is the synthetic of PPTA.
The fiber that is spun into by PPTA＜PPTA〉resin has been the most noticeable specialty synthetic fibre since the seventies, and its tensile strength height, tensile modulus are big, are widely used in space flight, aviation and other industrial sector.The PPTA resin is formed by Ursol D＜PPD〉and p-phthaloyl chloride＜TCl〉polycondensation, and its primitive reaction equation is as follows:
The common method that realizes this reaction is a low-temperature solution polycondensation.Be about to a kind of basic metal or alkaline earth salt as LiCl, CaCl
2, MgCl
2, LiCNS, KCNS etc.〉be dissolved in the amide solvent, form acid amides-single salts solution.The Ursol D of one of monomer is added in this kind solution, after the dissolving, in stirring, add another kind of monomer p-phthaloyl chloride.Be lower than 100 ℃, normal pressure stirs down, and reaction is until generate till the PPTA resin of suitable molecular weight.
Amide solvent commonly used in the low-temperature solution polycondensation has N-Methyl pyrrolidone＜NMP 〉, N, N'-N,N-DIMETHYLACETAMIDE＜DMA 〉, N, N'-diethyl acetamide＜DAA 〉, N-acetyl-pyrrolidine ketone and 1,3-dimethyl-2-imidazolone etc.Used basic metal or alkaline earth salt play solubilising, calcium chloride＜CaCl commonly used
2Or lithium chloride＜LiCl 〉.Difference according to salt in acid amides one single salts solution is referred to as " calcium method " and " lithium method " respectively.(see the Japanese patent application book, the spy opens clear 53-294, and the spy opens clear 53-11994).
In general, the CaCl of " calcium method "
2Consumption is 1.5～8%(wt%) of a NMP total amount, and optimum range is 4～8%(wt%).Problem is NMP-CaCl
2The solution system dissolving power is not strong, and polymkeric substance is easily separated out in polycondensation, is suspended in the solution, produces precipitation, results in blockage.Be mingled with not easy cleaning of calcium chloride in addition in the polymkeric substance, it is many, second-rate to cause polymkeric substance to close impurity, makes troubles to aftertreatment.The logarithmic specific concentration viscosity of the PPTA that produces with " calcium method " is generally 5～7.
" lithium method " is less with the lithium chloride amount, solvability is good, polymerization system is more stable, the lithium chloride that contains in the polymkeric substance＜LiCl〉is flush away easily, and aftertreatment is more convenient, and the fiber ash is few, the molecular weight height, narrow molecular weight distribution, the logarithmic specific concentration viscosity of the PPTA resin that usefulness lithium method is produced is generally 5.5～7.0, and shortcoming is that lithium chloride＜LiCl〉price comparison is expensive, operating restraint is narrow.
The objective of the invention is to seek a kind of acid amides-complex salt solution system, give full play to the advantage of " calcium method " and " lithium method ", overcome its deficiency, produce high-molecular weight PPTA resin with better processing condition.
Main points of the present invention are that synthetic PPTA is carried out in the complex salt solution system that a kind of alkaline earth metal halide of acid amides-a kind of basic metal forms, the halogenide consumption is 0.1%～5% of an acid amides weight, add pyridine and Ursol D (PPD), add p-phthaloyl chloride (TCl) then in two steps, a kind of monomeric concentration is 0.1～0.6mol/l, two kinds of monomer mole ratios are TCl/PPD=1～1.050, stir to make temperature of reaction remain on-10 ℃～80 ℃ under normal pressure.
Amide solvent used in the present invention can be N-Methyl pyrrolidone＜NMP 〉, N, N'-N,N-DIMETHYLACETAMIDE＜DMA 〉, N, N'-diethyl acetamide＜DAA 〉, N-acetyl-pyrrolidine ketone, 1,3-dimethyl-2-imidazolone.The double salt that employed alkali metal alkaline earth metal halogenide forms can be lithium chloride-calcium chloride (LiCl-CaCl
2), lithium chloride-magnesium chloride (LiCl-MgCl
2), lithium chloride-bariumchloride (LiCl-BaCl
2).
For example in polymerization reactor, add N-Methyl pyrrolidone, at N
2Under the protection, with CaCl
2Be added in the reactor with LiCl and pyridine, after salt dissolves fully, add monomer Ursol D (PPD), adding monomer p-phthaloyl chloride powder then at twice, is 40%～60% of total amount for the first time, 5～15 minutes at interval, quicken to stir, normal pressure keeps down react stopped reaction after 10 minutes between the temperature of reaction-10 ℃～80 ℃, must the pale yellow powder shaped polymer.Leave standstill then, elutriation, washing is filtered, drying, logarithmic specific concentration viscosity η inh is measured in the oven dry back.
At N-Methyl pyrrolidone-LiCl-CaCl
2Carry out the Ursol D p-phthaloyl chloride in the solution system when synthetic, should note controlling following condition:
1. the total consumption of calcium chloride-lithium chloride.The salt total amount that adds directly influences the solute effect of system, and then molecular weight is produced remarkably influenced.Because the complexing action of double salt in solvent increases solubilization-aid effect, so the total amount ratio of calcium chloride-lithium chloride is less, is preferably 0.5%～4% of N-Methyl pyrrolidone.
2. the ratio of calcium chloride-lithium chloride.The calcium chloride ratio is big, and the system solubility property is poor; The lithium chloride consumption is excessive, and then speed of response is fast, makes troubles to operation.The two ratio is improper, also can have influence on the effect of complexing.General CaCl preferably
2/ LiCl is 0.4～2.8(mole ratio).
3. monomer concentration.Monomer concentration is low excessively, and side reaction increases, and polymerization reactor and solvent utilization ratio are low excessively.Monomer concentration is too high, and solvent system is poorly soluble, because system viscosity is feeding-up, mixing, mass transfer, heat transfer all a difficult problem can occur simultaneously.A kind of monomeric concentration is preferably 0.25～0.55mol/l.
4. two kinds of monomer ratios.Because there are side reaction in p-phthaloyl chloride and solvent, with other impurity activity that also responds, so that this kind monomer is answered is more excessive, the scope of TCl/PPD is preferably 1.002～1.032(mole ratio).
5. add pyridine as sour accepting agent and solubility promoter, add-on be pyridine /～NH
2Be 0.60～1.20(mole ratio).
6. p-phthaloyl chloride is reinforced.For the ease of the control reaction, in time derive heat of polymerization, p-phthaloyl chloride should feed in raw material in two steps, and add-on is 40～60% of a total amount for the first time, is 60%～40% of total amount for the second time.
The present invention has reached and has given the phase effect.Owing to adopted acid amides-complex salt solution system to synthesize, strict control synthetic technological condition improves the molecular weight of polymer P PTA resin and logarithmic specific concentration viscosity, and logarithmic specific concentration viscosity can be stabilized in more than 7, reaches as high as 9～10.Compare with " calcium method ", gained molecular resin amount height, the system solvability is good, and impurity is few, and used total salt amount is few, and aftertreatment is simple.Compare with " lithium method ", operating restraint is wide, and cost is lower.
Be embodiments of the invention below.
Example one:
The 50mlN-methyl-2-pyrrolidone is added in the polymeric kettle, add 1.4321 gram calcium chloride (CaCl again
2) and 0.2623 grams lithium chloride (LiCl) and 1.0ml pyridine, at N
2Gas shiled adds 1.351 gram Ursol D down; add 1.2814 gram p-phthaloyl chlorides while stirring; react and add remaining 1.2814 gram p-phthaloyl chlorides after 5～20 minutes; reaction remains on 20 ℃～40 ℃; carried out 10～20 minutes, and obtained η inh at last and be 8.60 pale yellow powder shaped polymer.
Example two:
The 50mlN-methyl-2-pyrrolidone is put into polymeric kettle, add 1.6582 gram calcium chloride and 0.3741 grams lithium chloride and 0.5ml pyridines again, at N
2Protection adds 1.9465 gram Ursol D down; add 1.8455 gram p-phthaloyl chlorides while stirring; react and add remaining 1.8455 gram p-phthaloyl chlorides after 5～20 minutes; reaction keeps 20 ℃～40 ℃; carried out 10～20 minutes, and finally obtained η inh and be 9.50 pale yellow powder shaped polymer.
Example three:
The 50mlN-methyl-2-pyrrolidone is put into polymeric kettle, add 0.2076 gram calcium chloride and 0.1232 grams lithium chloride and 1ml pyridine again, at N
2Under the gas shiled; add Ursol D 0.8112 gram; under agitation add p-phthaloyl chloride 0.7637 gram; react after 5～20 minutes; add remaining 0.7637 gram p-phthaloyl chloride; reaction keeps 20 ℃～40 ℃, carries out 10～20 minutes, finally obtains η inh and be 7.12 pale yellow powder shaped polymer.
Be the comparative example of lithium chloride or calcium chloride list salts solution below:
Example four:
The 50mlN-methyl-2-pyrrolidone is put into polymeric kettle, add 1.1242 grams lithium chlorides and 2.5ml pyridine again, at N
2Under the gas shiled; add Ursol D 1.9465 grams; add p-phthaloyl chloride 1.8455 grams while stirring; react after 5～20 minutes; add remaining 1.8455 gram p-phthaloyl chlorides; reaction keeps 20 ℃～40 ℃, carries out 10～20 minutes, finally obtains η inh and be 5.75 pale yellow powder shaped polymer.
Example five:
The 50mlN-methyl-2-pyrrolidone is put into polymeric kettle, add 2.8364 gram calcium chloride and 2.8ml pyridines again, at N
2Under the gas shiled; add Ursol D 1.9465 grams; add p-phthaloyl chloride 1.8455 grams while stirring; react after 5～20 minutes; add remaining 1.8455 gram p-phthaloyl chlorides; reaction keeps 20 ℃～40 ℃, carries out 10～20 minutes, finally obtains η inh and be 5.14 pale yellow powder shaped polymer.
*Annotate: viscosity measurement
Use Ubbelohde viscometer, 98% vitriol oil is a solvent, concentration C=0.5 Grams Per Minute liter, 30 ℃ of probe temperatures.
T: the polymkeric substance sulphuric acid soln is through the capillary viscometer time;
t
o: 98% sulfuric acid stream is through the capillary viscometer time.
Claims (8)
1, Ursol D (PPD) and p-phthaloyl chloride (TCl) be synthetic PPTA in low temperature acid amides-salts solution, it is characterized in that solution system is the complex salt solution system that a kind of alkaline earth metal halide of acid amides-a kind of basic metal forms, the halogenide consumption is 0.1%～5% of an acid amides weight, add pyridine and Ursol D (PPD), add p-phthaloyl chloride (TCl) then in two steps, a kind of monomeric concentration is 0.1～0.6mol/l, two kinds of monomer mole ratios are TCl/PPD=1～1.050, stir to make temperature of reaction maintain-10 ℃～80 ℃ under normal pressure.
2, synthetic according to claim 1 is characterized in that said acid amides is a N-first pyrrolidone (NMP), N, N'-N,N-DIMETHYLACETAMIDE (DMA), N, N'-diethyl acetamide (DAA), N-acetyl-pyrrolidine ketone, 1,3-dimethyl-2-imidazolone.
3, synthetic according to claim 1 is characterized in that said halogenide is lithium chloride-calcium chloride (LiCl-CaCl
2), lithium chloride-magnesium chloride (LiCl-MgCl
2), lithium chloride-bariumchloride (LiCl-BaCl
2).
4, synthetic according to claim 1 is characterized in that said solution system is N-Methyl pyrrolidone-lithium chloride-calcium chloride (LiCl-CaCl
2) complex salt solution system.
5, synthetic according to claim 4, a kind of monomer concentration that is added in it is characterized in that reacting is 0.25～0.55mol/l, two kinds of monomer mole ratios are TCl/PPD=1.002～1.032.
6, synthetic according to claim 4 is characterized in that lithium chloride-calcium chloride total amount is 0.5%～4% of a N-Methyl pyrrolidone, CaCl
2/ LiCl is 0.4～2.8(mole ratio).
7, according to claim 1,4,5,6 synthetic, it is characterized in that said pyridine consumption be pyridine /～NH
2=0.60～1.20(mole ratio).
8, according to claim 1,4,5,6 synthesize is characterized in that the said p-phthaloyl chloride that adds in two steps is meant that add-on is 40～60% of a total amount for the first time, is 60%～40% of total amount for the second time, and twice reinforced 5～15 minutes at interval.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85100048A CN85100048B (en) | 1985-07-12 | 1985-07-12 | Synthesis of poly-phenylenetherephthalamide having high molecular weight |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85100048A CN85100048B (en) | 1985-07-12 | 1985-07-12 | Synthesis of poly-phenylenetherephthalamide having high molecular weight |
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| Publication Number | Publication Date |
|---|---|
| CN85100048A CN85100048A (en) | 1985-09-10 |
| CN85100048B true CN85100048B (en) | 1985-09-10 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN85100048A Expired CN85100048B (en) | 1985-07-12 | 1985-07-12 | Synthesis of poly-phenylenetherephthalamide having high molecular weight |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101476173B (en) * | 2009-01-20 | 2011-11-09 | 赵海鹏 | Direct spinning process for preparing PPTA fibre by end capping resin method |
| CN102649842A (en) * | 2012-05-11 | 2012-08-29 | 河南城建学院 | Method for synthesizing PPTA (poly-p-phenylene terephthamide) with high inherent viscosity |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456950B (en) * | 2008-10-28 | 2010-12-01 | 烟台氨纶股份有限公司 | Method for preparing high molecular weight poly(p-phenyleneterephthalamide) and products |
| CN110144636B (en) * | 2019-06-10 | 2021-09-24 | 黄河三角洲京博化工研究院有限公司 | Para-aramid fibrid and preparation method thereof |
| CN116023653B (en) * | 2023-03-29 | 2023-06-16 | 中化高性能纤维材料有限公司 | Method and system for continuously preparing para-aramid polymer |
-
1985
- 1985-07-12 CN CN85100048A patent/CN85100048B/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101476173B (en) * | 2009-01-20 | 2011-11-09 | 赵海鹏 | Direct spinning process for preparing PPTA fibre by end capping resin method |
| CN102649842A (en) * | 2012-05-11 | 2012-08-29 | 河南城建学院 | Method for synthesizing PPTA (poly-p-phenylene terephthamide) with high inherent viscosity |
| CN102649842B (en) * | 2012-05-11 | 2013-10-30 | 河南城建学院 | Method for synthesizing PPTA (poly-p-phenylene terephthamide) with high inherent viscosity |
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| Publication number | Publication date |
|---|---|
| CN85100048A (en) | 1985-09-10 |
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| C06 | Publication | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| CI02 | Correction of invention patent application | ||
| CI02 | Correction of invention patent application |
Correction item: Denomination of Invention Correct: Synthesis of benzene two benzoyl benzoyl two amine with high molecular weight False: the synthesis of high polymer poly (phenylene) two benzoyl - two - phenylene diamine |
|
| C14 | Grant of patent or utility model | ||
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Free format text: CORRECT FROM: ( INVENTION NAME )SYNTHESIS OF MACROMOLECULE PPTA TO: SYNTHESIS OF HIGH-MOLECULAR WEIGHT PPTA |
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| C19 | Lapse of patent right due to non-payment of the annual fee | ||
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